Novel reaction product of starches and aromatic acids and/or aromatic anhydrides

ABSTRACT

This invention relates to the reaction product of at least one starch with at least one aromatic anhydride and/or aromatic acid wherein the starch is reacted in the solid state with solid state reactants comprising the aromatic anhydride and/or aromatic acid, and at a time and temperature sufficient to obtain a reaction between the anhydride and/or acid.

RELATED APPLICATIONS

[0001] This application claims priority of provisional application U.S.Ser. No. 60/357,503 entitled “Starch Solid Stated With Acid orAnhydrides” filed on Feb. 15, 2002 and of U.S. Ser. No. ______ entitled“Novel Reaction Product of Starches and Aromatic Acids and/or AromaticAnhydrides” filed on Oct. 18, 2002.

FIELD OF THE INVENTION

[0002] The field of the invention relates to the reaction of at leastone starch with at least one aromatic anhydride and/or an aromatic acid.

BACKGROUND OF THE INVENTION

[0003] Starch based polymers have been known to be desirable for thedevelopment of food products, fibers, filaments, plastics, and otherproducts.

[0004] U.S. Pat. No. 4,212,704 (Durand et al.) discloses the reaction ofstarches with dibasic anhydrides (aromatic or aliphatic) in warm aqueousslurries prior to blending with clays, fibers, and possibly othermaterials in the manufacture of fiberboard. Durand et al. does not teachthe reaction of starches with anhydrides in the dry or solid state. Italso teaches the reaction of starches with anhydrides in the presence ofa base catalyst.

[0005] U.S. Pat. No. 2,461,139 teaches the treatment of starch, in thepresence of water, with organic acid anhydrides. This patent alsodiscloses that, previously, it had been considered impossible to reactstarch, in the presence of water, with organic acid anhydrides but thatan alkaline medium is essential.

[0006] U.S. Pat. No. 5,922,379 discloses starch phthalates.

[0007] Reactions of starches with aromatic anhydrides are generallyknown in the art. However, the reactions known in the art require eithera slurry of starch in water, an organic solvent or a base catalyst.

[0008] Many types of textile warp sizes have been used in the past. Inparticular, starch, starch derivatives, and animal glue have been usedin the case of cotton yarns, whereas polyvinyl alcohol has found wideacceptance as a size for yarns of synthetic materials, most commonlycellulose acetate and polyesters, such as polyethylene terephthalate,and blends of polyester fibers with cotton or rayon.

[0009] It is well known in the art that neither unmodified starches norstarches modified by acid hydrolysis, oxidation, ethoxylation,propoxylation, acylation with acetic anhydride, carboxymethylation orphosphation are suitable alone or in conjunction with non-film formingauxilaries for sizing spun textile yarns containing polyester. Typicallythe size formulation will contain either fully or partially hydrolyzedpolyvinyl alcohol. This compound will normally comprise anywhere from30-60% of the total solids in a size formula. The remainder of the sizemix being an unmodified or modified starch as previously described,binder (such as sodium polyacrylate,) humectant, and lubricant (normallyhydrogenated tallow glycerides.)

[0010] Polyvinyl alcohol is relatively expensive as compared to starchproducts, being as much as 5 times the cost of unmodified corn starch.It is generally understood that starch and the commercial modificationspreviously described do not adhere to polyester containing yarns wellenough to process the yarn into fabric without an impractical number ofbroken warp ends.

[0011] In view of the foregoing, it would be an advancement in the artto provide a novel and economical textile sizing agent with improvedadhesion to films, and to fibers and yarns, preferably to polyesterfibers and films and polyester containing fibers, yarns and films.Specifically, it is the modification of such starches by acylation witharomatic anhydrides and/or aromatic acids that assists in improvingthese adhesion properties. Moreover, it is the purpose to this inventionto replace part or all of the polyvinyl alcohol used to size such yarns,thereby providing improved economics to the sizing process.

SUMMARY OF THE INVENTION

[0012] In one aspect of this invention, there is provided a reactionproduct of at least one starch with at least one aromatic anhydrideand/or aromatic acid wherein the starch is reacted in the solid statewith solid state reactants comprising the aromatic anhydride and/oraromatic acid, in the absence of a base catalyst, at a time andtemperature sufficient to obtain a reaction between the aromaticanhydride and/or acid and the starch(es) to form an ester substituentgroup.

[0013] In a second aspect of the invention, there is provided a reactionproduct of at least one starch with at least one aromatic anhydrideand/or aromatic acid wherein the starch is reacted in the solid statewith solid state reactants comprising the aromatic anhydride and/oraromatic acid, and at a time and temperature sufficient to obtain areaction between the aromatic anhydride and/or acid and the starch(es)to form an ester substituent group; and wherein, during the solid statereaction, the solid state reactants have a total water content of 0 to6.0 weight % based on a total weight percentage for the solid statereactants of 100 weight %. In this embodiment, the presence of a basecatalyst is not necessary.

[0014] In a third aspect of the invention, a textile sizing agentcomprising the reaction products described above is provided. Thetextile sizing agents of the invention are preferably applied to yarnscontaining polyester fibers.

[0015] In a fourth aspect of the invention, a textile agent sized withthe reaction products of the invention is provided.

[0016] In a fifth aspect of the invention, a process for sizing atextile substrate material comprising applying to the textile material acomposition comprising the reaction products of the invention isprovided.

[0017] In a sixth aspect of the invention, a process for making amodified starch is provided comprising the step of reacting solid statereactants comprising at least one aromatic anhydride and/or aromaticacid with one or more starches in the solid state at a time andtemperature sufficient to obtain a reaction between the aromaticanhydride and/or acid and the starch(es) to form an ester substituentgroup; and wherein, during the solid state reaction, the solid statereactants have a total water content of 0 to 6.0 weight % based on thetotal weight percentage of the solid state reactants equaling 100 weight%. In this embodiment, the presence of a base catalyst is not necessary.

[0018] The present invention provides improved adhesion properties whenapplied as a textile sizing agent to fibers and/or yarn, preferablypolyester fibers and/or yarn either used alone or in combination withother types of fibers. The present invention also provides improvedadhesion properties when applied to polyester film.

DETAILED DESCRIPTION OF THE INVENTION

[0019] The invention relates primarily to the reaction product of atleast one starch in the solid state with solid state reactantscomprising at least one aromatic anhydride and/or aromatic acid. Thestarch is reacted in the solid state with the aromatic anhydride and/oraromatic acid or optionally, with other solid state reactants, at a timeand temperature sufficient to obtain a reaction between the anhydrideand/or acid and the starch(es) to form an ester substituent group. It ispreferred that the reaction proceeds without a base catalyst. It is alsopreferred that the reaction occur in the solid state. By “solid state”,it is meant that, during the reaction, the solid state reactants have atotal water content of 0.0 to 6.0% by weight, preferably less than 5.0%by weight, more preferably 0.1 to 4.0% by weight, and even morepreferably, less than 1.0% by weight, wherein the total weight of thesolid state reactants equals 100% by weight. By “total water content”,it is meant the sum of the water content of all of the solid statereactants present. This may be achieved by drying the reactants eitherseparately or together prior the solid state reaction. The time requiredto heat the reactor vessel and the reactants to the solid state reactiontemperature is not considered herein as part of the solid state reactiontime. It is preferred that no water be added during the solid statereaction. The weight % water in the solid state reactants is preferablyreduced to less than 0.1% by drying them separately at an elevatedtemperature prior to the solid state reaction. It is more preferred thatthe solid state reactants, preferably, the starch and aromatic anhydrideand/or aromatic acid, be dried separately at an elevated temperatureunder vacuum prior to the solid state reaction. The previously driedsolid state reactants (inclusive of the starch and the aromatic acidand/or anhydride) are then preferably mixed and heated at atmosphericpressure for a time and a temperature sufficient to obtain a reactionbetween the acid and/or anhydride and the starch to form an estersubstituent group. It is preferred that the solid state reactants of theinvention either consist essentially of or consist of starch andaromatic anhydride and/or aromatic acid and the total water content asdefined above for solid state conditions.

[0020] The starches useful in the present invention may be any starchknown in the art including, but not limited to, one or more starchesselected from corn starch, high amylose corn starch, potato starch,sweet potato starch, wheat starch, rice starch, tapioca starch, peastarch, rye starch, oat starch, sago starch and sorghum starch and theamylose and amylopectin fractions therefrom. It is preferred that thestarches be derived from rice, wheat, tapioca, potatoes, and/or corn.Wheat and corn sources are more preferred.

[0021] Although not required, it is also preferred that the starch be anacid modified starch and/or that it be in a granulated form. The sizesof the granules are typically from 3-100 microns with reference to theaverage size of their largest diameter. “Acid modified starch” refers toacid reaction with the starch prior to the reaction of the starch withthe aromatic anyhydride and/or aromatic acid. In a particular embodimentinvolving acid modification, the aqueous starch slurry is modified witha suitable acid such as hydrochloric or sulfuric acid at temperaturesbelow the gelatinization point. This occurs prior to the finaldewatering operation and after the starch is separated from the glutenand washed. The starch is then treated with 0.1 N acid (sulfuric orhydrochloric acid) at 40-50° C. for 6-24 hours, depending on the extentto modification or fluidity desired. The acid hydrolyzes α-1,6 and α-1,4glucosidic linkages. The reaction is stopped by addition of alkali suchas sodium carbonate. The final product is filtered, washed and dried.Examples of acid-modified starches particularly useful in the inventionare ANCHOR LR, CLINTON 221, CLINTON 240, and CLINTON 277, which are allcommercially available corn starches.

[0022] It is preferred that the number average molecular weight of thestarch is from 10,000 to 300,000, preferably 80,000 to 120,000.Anhydroglucose units of starch may have either a low or high degree ofester substitution (DS). DS as defined herein as applicable to anyfeature of the invention is the measure of degree of esterification ofthe three available hydroxyls of the anhydroglucose units of thestarch(es). The maximum DS is three.

[0023] The aromatic anhydride and/or aromatic acid of the invention maybe any aromatic anhydride known in the art but is preferably selectedfrom trimellitic anhydride, pyromellitic dianhydride (IUPAC name is1,2,4,5-benzenetetracarboxylic anhydride), and/or phthalic anhydride.Corresponding acids of the anhydrides may also be used. More preferably,the aromatic anhydride is phthalic anhydride. It is also preferable thatthe aromatic anhydride and/or aromatic acid is present in the reactionproduct of the invention in the amount of 0.05 to 6 weight %,preferably, 3.0-5.0 weight %, and more preferably, 3.8 to 4.2 weight %,wherein the total weight percentage of starch and aromatic anhydride oraromatic acid equals 100 weight %. It is also preferred that thearomatic anhydride and/or aromatic acid has a particle size of 2 mm orless.

[0024] While not being bound by any particular scientific theory, it isbelieved that the outer surface of the starch granule is reacted withthe aromatic anhydride and/or aromatic acid more substantially than theinner portion of said starch granule. As mentioned herein, the language“sufficient to form an ester substituent group” means that the finalreaction product has a resultant average degree of substitution (DS) ofat least 0.001 DS. The preferred resultant average degree ofsubstitution (DS) of the entire reaction product ranges between 0.001 to0.10, and more preferably, 0.001 to 0.07 (or stated another way, 0.03 to2.3% of the available hydroxyls on the anhydroglucose unit). The averageDS of the fraction of material on the outer surface has not beenestablished with certainty, but it could be as high as the theoreticalmaximum, i.e., 3.0, on some anhydroglucose units.

[0025] It is preferred that 2 to 60 g phthalic anhydride, morepreferably 10 to 50 g, even more preferably 36 to 42 g phthalicanhydride per 1000 g dry starch is used. While it is within the contextof this invention that the reaction occur at any time and temperaturesufficient to obtain a reaction between the anhydride or acid and thestarch to form an ester substituent group, it is preferred that thereaction time is from 5 to 120 minutes and that the reaction temperatureis from 250° F.±30° F. (121° C.±17° C.), preferably, that the reactiontime is from 100 to 120 minutes and the reaction temperature is about250° F. (121° C.), and more preferably, that the reaction time is from20 to 30 minutes and the reaction temperature is from 265° F.±15° F.(129°±9° C.).

[0026] While it is not preferable in one aspect of the invention to havea base present in the solid state reaction of the invention, it ispreferred to add a base to the final reaction product to react with theunreacted aromatic anhydride or aromatic acid or carboxylic acid forsafety and handling reasons. By “absence of base catalyst or no basecatalyst”, it is meant that no base is present during the solid statereaction of the invention. Although any base known in the art may beused, it is preferable that the base be selected from the groupconsisting of ammonia, aqua ammonia, amines, polyamines and aminoalcohols. Other known bases can be used as well such as but not limitedto potash, potassium hydroxide, soda ash, sodium hydroxide, lithiumhydroxide, or trisodium phosphate. The base preferably reacts with anyunreacted phthalic anhydride or phthalic acid or carboxylic acid. Theaddition of base after the solid state reaction is optionally performeddue to environmental reasons.

[0027] Although the mixing or blending of the starch(es) and thearomatic anhydride and/or aromatic acid may be accomplished by any meansknown in the art, it is preferred also that the starting materials aremixed in a dry blender during the reaction.

[0028] An important embodiment of this invention is the use of thereaction products of the invention as textile sizing agents. Also, anembodiment of the invention is the application of one of the reactionproducts of the invention to a textile substrate material or textilematerial. Another embodiment of the invention is textile yarn sized witha textile sizing agent comprising or consisting essentially of one ofthe reaction products of the invention.

[0029] The textile fibers, textile material, textile substrate materialof textile yarn (all terms used equivalently) of the invention may beselected from polyester, cotton, polyacrylics, polyamides, polyolefins,rayons, and wool. Preferably, it is a polyester or a blend of one ormore polyesters with at least one of the following: cotton,polyacrylics, polyamides, polyolefins, rayons and wool.

[0030] The polyesters useful in the invention comprise diacid residuesand diol residues. Useful dicarboxylic acids include but are not limitedto ones having from 6 to about 40 carbon atoms, and more preferablydicarboxylic acids selected from aromatic dicarboxylic acids preferablyhaving 8 to 14 carbon atoms, aliphatic dicarboxylic acids preferablyhaving 4 to 12 carbon atoms, or cycloaliphatic dicarboxylic acidspreferably having 7 to 12 carbon atoms. Examples of suitabledicarboxylic acids include terephthalic acid, isophthalic acid,5-sodiosulfoisophthalic acid, phthalic acid, naphthalenedicarboxylicacid, 1,4-cyclohexanedicarboxylic acid, cyclohexanediacetic acid,diphenyl-4,4′-dicarboxylic acid, succinic acid, glutaric acid, adipicacid, azelaic acid, sebacic acid, and the like. The various isomers ofnaphthalenedicarboxylic acid or mixtures of isomers may be used, but the1,4-, 1,5-, 2,6-, and 2,7-isomers are preferred. The1,4-cyclohexanedicarboxylic acid may be in the form of cis, trans, orcis/trans mixtures. In addition, for purposes of this invention,“dicarboxylic acid” includes the lower alkyl ester or acid halide formof the diacid. Further, these ester and acid chloride forms may also beused in place of or in conjunction with the diacid form. Polyesters maybe prepared from one or more of the above dicarboxylic acids.

[0031] Typical glycols used in the polyester fibers, film and/or yarn ofthe invention include aliphatic glycols containing from two to about tencarbon atoms, and cycloaliphatic glycols containing 7 to 14 carbonatoms. Preferred glycols include ethylene glycol, propylene glycol,1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, diethyleneglycol and the like. The glycol component may optionally be modifiedwith up to about 50 mole %, preferably up to about 25 mole %, and morepreferably up to about 15 mole % of one or more different diols. Suchadditional diols include cycloaliphatic diols preferably having 6 to 20carbon atoms, aromatic diols containing from 6 to 15 carbon atoms oraliphatic diols preferably having 3 to 20 carbon atoms. Examples of suchdiols include: diethylene glycol, triethylene glycol, trimethyleneglycol, 1,4-cyclohexanedimethanol, propane-1,3-diol, butane-1,4-diol,pentane-1,5-diol, 2-methylpentanediol-(1,4),2,2,4-trimethylpentane-diol-(1,3), 2-ethylhexanediol-(1,3),2,2-diethylpropane-diol-(1,3), hexanediol-(1,3),1,4-di-(2-hydroxyethoxy)-benzene, 2,2-bis-(4-hydroxycyclohexyl)-propane,2,4-dihydroxy-1,1,3,3-tetramethylcyclobutane,2,2-bis-(3-hydroxyethoxyphenyl)-propane,2,2-bis-(4-hydroxypropoxyphenyl)-propane, resorcinol, hydroquinone,catechol, bisphenol and its derivatives, and the like. Polyesters may beprepared from one or more of the above diols.

[0032] While any polyester may be useful in this invention, a preferredembodiment of the invention relates to a residue of a glycolic componentcomprising ethylene glycol and polyester comprising a residue of adicarboxylic acid comprising terephthlalic acid. The dicarboxylic acidcomponent of the polyester may optionally be modified with up to about50 mole % and, optionally, up to about 20 mole % of one or moredifferent carboxylic acids.

[0033] In one aspect of the invention, the polyester useful in thefibers, films or yarns of this invention comprises 80 to 100 mole %terephthalic acid residues and 100 to 80 mole % ethylene glycol, morepreferably, 90 to 100 mole % terephthalic acid residues and 100 to 90mole % ethylene glycol, wherein the total mole percentages of the glycolcomponent equal 100 mole % and the total mole percentages of the acidcomponent equal 100 mole %. Poly(ethylene terephthalate) such as thatsold in fiber form under the Dacron™ trademark and in film form underthe Mylar™ trademark is particularly useful in this invention.

[0034] In another aspect of the invention, the polyester useful in thefibers, films or yarns of this invention comprises 80 to 100 mole %terephthalic acid residues and 100 to 80 mole %1,4-cyclohexanedimethanol residues; more preferably, 90 to 100 mole %terephthalic acid residues and 100 to 90 mole %1,4-cyclohexanedimethanol residues; wherein the total mole percentagesof the glycol component equal 100 mole % and the total mole percentagesof the acid component equal 100 mole %.

[0035] In yet another aspect of the invention, the polyester useful inthe fibers, films or yarns of this invention comprises 80 to 100 mole %terephthalic acid residues, 10 to 50 mole % 1,4-cyclohexanedimethanol,and 90 to 50 mole % ethylene glycol; more preferably, 90 to 100 mole %terephthalic acid residues, 20 to 40 mole % 1,4-cyclohexanedimethanol,and 80 to 60 mole % ethylene glycol; and even more preferably, 90 to 100mole % terephthalic acid residues, 28 to 35 mole %1,4-cyclohexanedimethanol residues, and 72 to 65 mole % ethylene glycolresidues; wherein the total mole percentages of the glycol componentequal 100 mole % and the total mole percentages of the acid componentequal 100 mole %.

[0036] The polyesters useful in the fibers, films or yarns useful in thepresent invention are formed via conventional polyesterification andpolycondensation techniques. Typical methods for preparing thesepolyesters are described in U.S. Pat. Nos. 2,465,319 and 3,047,539. Anytypical additive known in the art may be present in the polyesters ofthe present invention. Howver, polyesters useful in this invention maybe made by any of several methods known in the art.

[0037] The textile sizing agents of the invention comprise the reactionproducts of the invention. The textile sizing agents of the inventionare in turn useful in sizing the textile fibers, textile materials,textile substrates or textile yarns of the invention. When applied tosuch fibers, materials or yarn, particularly in the case of polyesterfibers blended with other fibers, the textile sizing agent has improvedadhesive properties.

[0038] The esterified starches, which comprise the reaction products ofthe invention, may be formulated with any such additives as are known inthe art. However, preferred additives include ones commonly incorporatedinto textiles. Such preferred additives include, but are not limited to,acrylic, urethane or polyester resins or binders, lubricants, waxes,biocides, flame retardants, fillers, pigments, dyes, softeners,post-added surfactants, catalysts, and cross-linking agents. Acombination of additives may also be used.

[0039] The processes of the invention comprise applying the reactionproduct of the invention to a textile substrate material as well as aprocess for the manufacture of the reaction product of the invention.Although the process of manufacture of the invention contains parametersas already described herein, it is preferred that the followingparticulars be used. For the purposes of description for the followingpreferred embodiment of the invention, starch and phthalic anhydride areused as examples. First, the starch must be charged to the mixer.Typically the starch has a water content of 7.0 to 12.0% based on thetotal weight of the starch. The starch is heated in the dry blenderuntil the water content is 6% or less. One example is to heat the starchalone in the heated dry blender to 200° F.-220° F. (93° C. to 105° C.)to approximately 1% or less water content. The agitation is controlledat this step so as to minimize the amount of dust generated in the headspace It is preferred that a vaccum be used to expedite the dryingprocess of the starch by allowing water to be taken from the blenderuntil a water content of 0-6.0% by weight of the total weight (100weight %) of the starch is obtained, preferably less than 5%, morepreferably, 0.01-4.0%, and even more preferably 0.01-2.0%, mostpreferably, less than 1.0%. Next, ground phthalic anhydride is added tothe extent of 0.2 to 6 weight %, preferably, 1.0-5.0 weight %, and morepreferably, 3.0-5.0 weight %, and even more preferably, 3.6 -4.2 weight%, based on 100 weight % total of starch and phthalic anhydride. The mixis heated with agitation at atmospheric pressure to reactiontemperature. It is preferred that the reaction time is from 5 to 120minutes and that the reaction temperature is from 250° F.±30° F. (121°C.±17° C.), preferably, that the reaction time is from 100 to 120minutes and the reaction temperature is about 250° F. (121° C.), andmore preferably, that the reaction time is from 20 to 30 minutes and thereaction temperature is from 265° F.±15° F. (129° C.±9° C.).

[0040] The mixer is then cooled to 100° F. to 110° F. (38° C. to 43°C.). The reaction product is neutralized with dilute ammonia in anamount sufficient to react with the unreacted phthalic anhydride,typically from 1-75% of the initial amount charged. The neutralizationis mainly performed due to health, safety and/or environmental reasons.It is not necessary for the satisfactory performance of the reactionproduct.

[0041] This invention can be further illustrated by the followingexamples of preferred embodiments thereof, although it will beunderstood that these examples are included merely for purposes ofillustration and are not intended to limit the scope of the inventionunless otherwise specifically indicated.

EXAMPLES Example 1

[0042] The following example illustrates the pilot scale treatment ofthe preferred aromatic anhydride (phthalic anhydride) with unmodifiedcorn starch. 67.5 pounds of CLINTON 106 corn strarch are charged to aLiftleford Ploughshare reactor preheated to an incoming steam jackettemperature of about 320° F. (160° C.). The resultant internaltemperature is about 300° F. The ploughblade mixer is started, adjustedto half speed, and the vacuum is initiated while simultaneously heatingto 222° F. (105° C.) at −25 inches of mercury gauge pressure. Once thistemperature and pressure are achieved, a sample is taken. The starch isheld at temperature until the water is determined to be 0.5% or less asmeasured by an electronic water balance. The vacuum is removed, and 2.5pounds of 65 mesh phthalic anhydride are charged through the stack.Filter bags are placed over the stack, and an internal chopper or baffleblade mixer is turned on. The temperature is raised to 250-260° F. (121°C.-127° C.) over 30 minutes and held for one hour. The steam jacket isblown down, the chopper discontinued, and the product is cooled to 130°F. (54° C.). Next, 12.6 pounds of 2.2% ammonia are charged by aninternal spray head. The product is cooled below 110° F. (43° C.) anddischarged as a free-flowing powder. The resultant pH of a 5% dispersionis 8-9. Adhesion of the acylated starch to MYLAR polyester film is good.

Example 2

[0043] The procedure used in Example 1 is repeated, where the anhydrideused is trimellitic. Adhesion of the acylated starch to MYLAR polyesterfilm is good.

Example 3

[0044] This example illustrates the lab preparation of said acylatedstarch using a small laboratory version of the Littleford Ploughshareblender. To said mixer, 1148 grams of CLINTON 277 acid-modified cornstarch is charged. The vent cover is placed on the top without filterand the starch is agitated slowly while heating up using 13 psig steampressure. The starch is held at 200-220° F. (93° C.-104° C.) for twohours and effectively 99% dry. The agitation is turned off, and 44.5grams of ground phthalic anhydride is added to the unit. The vent box isreplaced along with cellulose filter screens. The agitation is turned onthree-quarter speed and the mixture is heated to 235-250° F. (113°C.-121° C.) and held for two hours. The mixture is cooled to 100° F.(38° C.) and discharged. Adhesion of the acylated starch to MYLARpolyester film is good.

Example 4

[0045] The procedure used in Example 3 is repeated where the anhydrideused is pyromellitic anhydride. Adhesion of the acylated starch to MYLARpolyester film is good.

Example 5

[0046] The product produced by Example 3 neutralized by 2.2% ammonia topH 3-9. Adhesion to the acylated starch to MYLAR polyester film is good.

Example 6

[0047] The product produced by Example 4 neutralized by 20%triethanolamine to pH 3-9. Adhesion of the acylated starch to MYLARpolyester film is good.

Examples 7-15 (Table 1)

[0048] In each of the above examples (1-6) and in each of the examplesbelow (7-15) the acylated starch was slurried in water at 5% solids andheated with good agitation to just below the boiling temperature for 15minutes to “cook out” the starch, i.e., to heat above the gelatinizationtemperature of the starch. After the 15 minute hold, the resultingslurry was cooled to about 85° C. Aliquots of the slurry weretransferred to and drawn down on a clean sheet of MYLAR polyester filmwith a 40-mil Bird type film applicator. After drying at roomtemperature overnight, the adhesion of the starch film to the MYLARpolyester sheet was measured by repeatedly scraping the starch film witha knife blade. (Good adhesion to MYLAR polyester film is taken as anindication that the starch will also have improved adhesion to textilefibers and yarns containing polyester fibers.) The adhesion ratingsystem used was as follows:

[0049] 1=poor adhesion

[0050] 2=marginal adhesion

[0051] 3=fair adhesion

[0052] 4=good adhesion

[0053] 5=excellent adhesion TABLE 1 Effect of Water Level, ReactionTemperature and Reaction Time on Adhesion to Polyester Starch TypePhthalic Reaction Reaction Example Corn (Alkali Water, Anhydride, TSP,Temp. Time, Adhesion No. Starch Fluidity) % % % ° C. Hr. Rating 7Clinton Pearl 5 4.0 4 60-70 2 2 106 (0) 8 Clinton Pearl 5 4.0 0 60-70 23 106 (0) 9 Clinton Acid- 5 4.0 4 60-70 2 2 277 modified (80) 10 ClintonAcid- 5 4.0 0 60-70 2 3 277 modified (80) 11 Clinton Acid- <1 4.4 0110-113 2 4 277 modified (80) 12 Clinton Acid- <1 4.4 0 110-113 2 4 277modified (80) 13 Clinton Acid- <1 4.4 0 121-129 0.5 4 240 modified (40)14 Clinton Acid- <1 4.4 0 121-129 0.5 4 277 modified (80) 15 ClintonAcid- 12 0 0 Not 0 1 277 modified heated (80) #Unmodified starch has anAlkali Fluidity value of zero indicating no flow through the orifice in70 seconds. As the starch is converted, its flow value increases. Wateralone has an Alkali Fluidity (flow value) of 100 seconds, indicating 100milliliters delivered through the standard orifice in 70 seconds.

[0054] Examples 7-10 in Table 1 show that, at a Water % of 5%, there isno beneficial effect on adhesion of the phthalated starch to MYLARpolyester film obtained by including an alkali (TSP) in the solid-statereaction mix. In fact, the inclusion of TSP seems to have a slightlydeleterious effect on adhesion.

[0055] Examples 11-15 show the beneficial effect of reducing the waterlevel of the starch (acid-modified starch in this case) to much belowthe 5% level. Reducing the water level to less than 1% improves theadhesion of the resulting phthalated starch from a 3 rating (“fair”adhesion) to a 4 rating (“good” adhesion). Inclusion of an alkali is notrequired to achieve this improvement.

[0056] Examples 13 and 14 illustrate how reaction time can be greatlyreduced by increasing reaction temperature by only about 10° C. to 15°C.

[0057] Example 15 shows, by comparison with Examples 7-14, the pooradhesion to MYLAR polyester substrate of starch that has not beenacylated with an aromatic anhydride by the practice of the presentinvention.

[0058] The utility of acylated starches of this invention isdemonstrated by sizing a polyester/cotton yarn with a dispersion of theacylated starch in water, drying the yarn and testing the abrasionresistance of the sized yarn. For the examples in Table 2, a 65/35polyester/cotton yarn (26/1 cotton count) is sized with the phthalatedstarches of examples 16-22 and tested for abrasion resistance on alaboratory device that simulates the abrasive action that yarnsexperience in weaving. The number of abrasion cycles of the machinerequired to break the yarn is recorded; the greater the number ofcycles, the greater the abrasion resistance of the sized yarn. TABLE 2Reactions with Phthalic Anhydride* Reaction Reaction Example StarchWater, Temp., Time, Adhesion Abrasion No. Starch Type % ° C. hr. RatingCycle 16 Clinton 106 Pearl 11 110-113 2 2 159 17 Clinton 106 Pearl 6110-113 2 3 250 18 Clinton 106 Pearl <0.1 110-113 2 4 344 19 Clinton 106Pearl <0.1 121-129 0.5 4 444 20 Clinton 277 Acid- <0.1 121-129 0.5 41099 modified 21 Clinton 211 Acid- <0.1 110-113 2 4 1196 modified 22Clinton 277 Acid- <0.1 110-113 2 4 1635 modified

[0059] Examples 16-18 show the positive effect of reducing the watercontent of the starch. Adhesion rating and abrasion resistance (of sizedpolyester/cotton yarn) increases as initial water level of the starchdecreases. The polyester fiber in the polyester cotton yarn used inExamples 16-22 is polyethylene terephthalate or PET polyester. This isthe same polyester used to make MYLAR polyester film. No TSP or otheralkali is included in the solid state phthalations of Examples 16-22.

[0060] Example 23-Example 20 is repeated except phthalic acid issubstituted for phthalic anhydride. The adhesion rating of the resultingacylated starch is 4 and the number of abrasion cycles is 1015.

[0061] The invention has been described in detail with particularreference to preferred embodiments thereof, but it will be understoodthat variations and modifications can be effected within the spirit andscope of the invention. The present invention is further represented bythe following claims.

We claim:
 1. A reaction product of at least one starch with at least onearomatic anhydride and/or aromatic acid wherein said starch is reactedin the solid state with solid state reactants comprising said aromaticanhydride and/or aromatic acid, in the absence of a base catalyst, andat a time and temperature sufficient to obtain a reaction between saidanhydride and/or acid and said starch(es) to form an ester substituentgroup.
 2. The reaction product of claim 1 wherein said starch is derivedfrom rice, wheat, tapioca, potatoes, and/or corn.
 3. The reactionproduct of claim 1 herein said starch is acid-modified prior to saidsolid state reaction.
 4. The reaction product of claim 1 wherein saidstarch is in a granulated form.
 5. The reaction product of claim 1wherein the number average molecular weight of the starch is10,000-300,000.
 6. The reaction product of claim 1 wherein the numberaverage molecular weight of the starch is 80,000-120,000.
 7. Thereaction product of claim 1 wherein said aromatic anhydride and/oraromatic acid is present in the amount of 0.05 to 6 weight % and whereinthe total weight percentage of starch and anhydride or acid equals 100weight %.
 8. The reaction product of claim 7 wherein said aromaticanhydride and/or aromatic acid is present in the amount of 3.0 to 5.0weight %.
 9. The reaction product of claim 1 wherein said aromaticanhydride initially has a particle size of 2 mm or less. 10 The reactionproduct of claim 1 wherein said aromatic anhydride is selected from thegroup consisting of trimellitic anhydride, pyromellitic dianhydride andphthalic anhydride.
 11. The reaction product of claim 10 wherein saidaromatic anhydride is phthalic anhydride.
 12. The reaction product ofclaim 1 having a D.S. of 0.001 to 0.10.
 13. The reaction product ofclaim 7 having a D.S. of 0.001 to 0.07.
 14. The reaction product ofclaim 1 wherein, during the solid state reaction, said solid statereactants have a total water content of 0 to 6.0 weight % based on atotal weight percentage for the solid state reactants of 100% weight %.15. The reaction product of claim 14 wherein said solid state reactantshave a total water content of 0.1 to 4.0% weight %.
 16. The reactionproduct of claim 14 wherein said solid state reactants have a totalwater content of less than 1.0% weight %.
 17. The reaction product ofclaim 1 wherein a base is added to the final reaction product to reactwith unreacted aromatic anhydride or aromatic acid.
 18. The reactionproduct of claim 17 wherein said base is selected from the groupconsisting of ammonia, aqua ammonia, amines, polyamines, andaminoalcohols.
 19. The reaction product of claim 1 wherein said at leastone starch and said at least one aromatic anhydride and/or aromatic acidare mixed in a dry blender during the reaction.
 20. A reaction productof at least one starch with at least one aromatic anhydride and/oraromatic acid wherein said starch is reacted in the solid state withsolid state reactants comprising said aromatic anhydride and/or aromaticacid, and at a time and temperature sufficient to obtain a reactionbetween said anhydride and/or acid and said starch(es) to form an estersubstituent group; and wherein, during said solid state reaction, saidsolid state reactants have a total water content of 0 to 6.0 weight %based on a total weight percentage.
 21. The reaction product of claim 20wherein said starch is derived from rice, wheat, tapioca, potatoes,and/or corn.
 22. The reaction product of claim 20 wherein said starch isacid-modified prior to said solid state reaction.
 23. The reactionproduct of claim 20 wherein said starch is in a granulated form.
 24. Thereaction product of claim 20 wherein the number average molecular weightof the starch is 10,000-300,000.
 25. The reaction product of claim 24wherein the number average molecular weight of the starch is80,000-120,000.
 26. The reaction product of claim 1 wherein saidaromatic anhydride and/or aromatic acid is present in the amount of 0.05to 6 weight % and wherein the total weight percentage of starch andanhydride or acid equals 100 weight %.
 27. The reaction product of claim20 wherein said aromatic anhydride and/or aromatic acid is present inthe amount of 3.0 to 5.0 weight %.
 28. The reaction product of claim 20wherein said aromatic anhydride initially has a particle size of 2 mm orless.
 29. The reaction product of claim 20 wherein said aromaticanhydride is selected from the group consisting of trimelliticanhydride, pyromellitic dianhydride and phthalic anhydride.
 30. Thereaction product of claim 20 wherein said aromatic anhydride is phthalicanhydride.
 31. The reaction product of claim 20 having a D.S. of 0.001to 0.10.
 32. The reaction product of claim 20 having a D.S. of 0.001 to0.07.
 33. The reaction product of claim 20 wherein said solid statereactants have a water content of less than 5.0% by weight.
 34. Thereaction product of claim 20 wherein said solid state reactants have atotal water content of 0.1-4.0% by weight.
 35. The reaction product ofclaim 20 wherein said solid state reactants have a total water contentof less than 1.0% by weight.
 36. The reaction product of claim 20wherein said at least one starch and said at least one aromaticanhydride and/or aromatic acid are mixed in a dry blender during thereaction.
 37. A textile sizing agent comprising the reaction product ofat least one starch with at least one aromatic anhydride and/or aromaticacid wherein said starch is reacted in the solid state with solid statereactants comprising said aromatic anhydride and/or aromatic acid, inthe absence of a base catalyst, and at a time and temperature sufficientto obtain a reaction between said anhydride and/or acid and saidstarch(es) to form an ester substituent group.
 38. A textile sizingagent comprising the reaction product of at least one starch with atleast one aromatic anhydride and/or aromatic acid wherein said starch isreacted in the solid state with solid state reactants comprising saidaromatic anhydride and/or aromatic acid, and at a time and temperaturesufficient to obtain a reaction between said anhydride and/or acid andsaid starch(es) to form an ester substituent group; and wherein, duringsaid solid state reaction, said solid state reactants have a total watercontent of 0 to 6.0 weight % based on a total weight percentage of 100weight %.
 39. A textile sizing agent for polyester fibers andpolyester-containing yarn comprising the reaction product of at leastone starch with at least one aromatic anhydride and/or aromatic acidwherein said starch is reacted in the solid state with solid statereactants comprising said aromatic anhydride and/or aromatic acid, inthe absence of a base catalyst, and at a time and temperature sufficientto obtain a reaction between said anhydride and/or acid and saidstarch(es) to form an ester substituent group.
 40. A textile sizingagent for polyester fibers and polyester-containing yarn comprising thereaction product of at least one starch with at least one aromaticanhydride and/or aromatic acid wherein said starch is reacted in thesolid state with solid state reactants comprising said aromaticanhydride and/or aromatic acid, and at a time and temperature sufficientto obtain a reaction between said anhydride and/or acid and saidstarch(es) to form an ester substituent group; and wherein, during saidsolid state reaction, said solid state reactants have a total watercontent of 0 to 6.0 weight % based on a total weight percentage of 100weight %.
 41. A textile yarn sized with the textile sizing agents ofclaims 37 and
 38. 42. The textile yarn of claim 41 comprising one ormore polyesters.
 43. The textile yarn of claim 42 wherein said one ormore polyesters comprise 80 to 100 mole % terephthalic acid residues and100 to 80 mole % ethylene glycol wherein the total mole percentages ofthe glycol component equals 100 mole % and the total mole percentages ofthe acid component equals 100 mole %.
 44. The textile yarn of claim 43comprising poly(ethylene terephthalate).
 45. The textile yarn of claim42 wherein said one or more polyesters comprise 80 to 100 mole %terephthalic acid residues and 100 to 80 mole %1,4-cyclohexanedimethanol wherein the total mole percentages of theglycol component equals 100 mole % and the total mole percentages of theacid component equals 100 mole %.
 46. The textile yarn of claim 42wherein said one or more polyesters comprise 80 to 100 mole %terephthalic acid residues, 10 to 50 mole % 1,4-cyclohexanedimethanolresidues, and 90 to 50 mole % ethylene glycol residues, wherein thetotal mole percentages of the glycol component equals 100 mole % and thetotal mole percentages of the acid component equals 100 mole %.
 47. Thetextile yarn of claim 41 comprising a blend of polyester fibers andfibers selected from the group consisting of cotton, polyacrylics,polyolefins, rayons, and wool.
 48. A process for sizing a textilesubstrate material comprising applying to the textile material acomposition comprising the reaction product of claims 1 and
 20. 49. Theprocess of claim 45 wherein said textile substrate material comprisesone or more polyesters.
 50. The process of claim 49 wherein said one ormore polyesters comprising 80 to 100 mole % terephthalic acid residuesand 100 to 80 mole % ethylene glycol wherein the total mole percentagesof the glycol component equals 100 mole % and the total mole percentagesof the acid component equals 100 mole %.
 51. The textile yarn of claim49 wherein said one or more polyesters comprise 80 to 100 mole %terephthalic acid residues and 100 to 80 mole %1,4-cyclohexanedimethanol wherein the total mole percentages of theglycol component equals 100 mole % and the total mole percentages of theacid component equals 100 mole %.
 52. The textile yarn of claim 49wherein said one or more polyesters comprise 80 to 100 mole %terephthalic acid residues, 10 to 50 mole % 1,4-cyclohexanedimethanolresidues, and 90 to 50 mole % ethylene glycol residues, wherein thetotal mole percentages of the glycol component equals 100 mole % and thetotal mole percentages of the acid component equals 100 mole %.
 53. Theprocess of claim 49 comprising a blend of polyester fibers and fibersselected from the group consisting of cotton, polyacrylics, polyolefins,rayons, and wool.
 54. The process of reacting at least one starch withat least one aromatic anhydride and/or aromatic acid wherein said starchis reacted in the solid state with solid state reactants comprising saidaromatic anhydride and/or aromatic acid, in the absence of a basecatalyst, and at a time and temperature sufficient to obtain a reactionbetween said anhydride and/or acid and said starch(es) to form an estersubstituent group.
 55. The process of reacting at least one starch withat least one aromatic anhydride and/or aromatic acid wherein said starchis reacted in the solid state with solid state reactants comprising saidaromatic anhydride and/or aromatic acid, and at a time and temperaturesufficient to obtain a reaction between said anhydride and/or acid andsaid starch(es) to form an ester substituent group; and wherein, duringsaid solid state reaction, the solid state reactants have a total watercontent of 0 to 6.0 weight % based on a total weight percentage of 100weight %.
 56. The process of claim 55 wherein said starch and aromaticanhydride or aromatic acid are dried prior to the solid state reactionto a water content of 0.1 to 4.0 weight %.
 57. The process of claim 56wherein said starch and aromatic anhydride or aromatic acid are driedprior to the solid state reaction to a water content of less than 1weight %.
 58. The process of claim 56 wherein said starch and aromaticanhydride or aromatic acid are dried under vacuum where said temperatureis increased to the initial reaction temperature.